Green Glyphosate Treatment with Ferrihydrite and CaO<sub>2</sub> via Forming Surface Ternary Complex
Nuanqin Zhang, Hongwei Sun, Guangming Zhan, Junning Zu, Lizhi Zhang
Abstract
Glyphosate (PMG) is a globally used broad-spectrum herbicide and receives environmental concerns because of its moderate persistence and potential carcinogenicity. Traditional PMG treatment methods often suffer from the generation of a more toxic and persistent aminomethylphosphonic acid (AMPA) intermediate. Herein, we develop a green method with ferrihydrite (FH) and CaO 2 (FH/CaO 2 ) via regulating the coordination of PMG with FH and Ca 2+, where the phosphonate group of PMG preferentially binds to FH and its carboxylate side complexes with Ca 2+ released by CaO 2, forming a FH-PMG-Ca ternary surface complex. This unique ternary complex can redistribute electrons within the PMG molecule for its C–P activation and C–N bond stabilization, favoring the selective C–P bond attack of superoxide radical produced by the Fenton reaction between CaO 2 -derived H 2 O 2 and FH, thus generating environment-friendly glycine instead of AMPA. The FH/CaO 2 process realizes over 99% PMG degradation in industrial wastewater within 1 h, with residual PMG < 0.1 ppm and AMPA < 40 ppb. More importantly, the CaO 2 consumption was as low as 3.1 mg of CaO 2 /mg of PMG, one-fifth those of previously reported CaO 2 -based counterparts. This study provides an effective and environment-friendly PMG treatment strategy and highlights the importance of surface coordination modes on the degradation pathway of PMG.